Hydrogen transport through amorphous Pd82-yNiySi18 alloys (y = 0-32) was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. It was found that the anodic current transient shows the non-Cottrell behaviour, but its shape and value remain nearly constant regardless of the hydrogen discharging potential. From the coincidence of the anodic current transient theoretically calculated with that experimentally measured, it is suggested that the change in surface concentration of hydrogen with time is uniquely given by the rate of hydrogen transfer from absorbed state at the electrode sub-surface to adsorbed state on the electrode surface. This means that neither the 'constraint of constant concentration' nor the 'constraint by Butler-Volmer behaviour' is effective at the electrode surface during hydrogen extraction. On the basis of the theoretical current-time relation under the 'constraint by hydrogen transfer of absorbed state to adsorbed state', the hydrogen diffusivity was determined to have an almost constant value of (1.3 +/- 0.4) x 10(-8) cm(2) s(-1), irrespective of the Ni content and in the absence of Ni. On the other hand, it is inferred that the rate constant of hydrogen transfer decreases markedly with increasing Ni content due to the Ni(OH)(2) layer formed on the electrode surface. (C) 2003 Elsevier Science Ltd. All rights reserved.